WO2011033988A1 - 芳香族ポリエステル - Google Patents

芳香族ポリエステル Download PDF

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Publication number
WO2011033988A1
WO2011033988A1 PCT/JP2010/065535 JP2010065535W WO2011033988A1 WO 2011033988 A1 WO2011033988 A1 WO 2011033988A1 JP 2010065535 W JP2010065535 W JP 2010065535W WO 2011033988 A1 WO2011033988 A1 WO 2011033988A1
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Prior art keywords
group
acid
aromatic polyester
aromatic
dimethyl
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English (en)
French (fr)
Japanese (ja)
Inventor
昌祥 田畑
康輝 馬渡
隆喜 山崎
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Nitta Corp
Muroran Institute of Technology NUC
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Nitta Corp
Muroran Institute of Technology NUC
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Priority to US13/496,215 priority Critical patent/US20120172570A1/en
Priority to EP10817101A priority patent/EP2479203A1/en
Publication of WO2011033988A1 publication Critical patent/WO2011033988A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings

Definitions

  • the present invention relates to an aromatic polyester, and more particularly to an aromatic polyester used for optical applications.
  • the polymerization reaction temperature is 160 to 320 ° C. in the initial stage of polymerization, and after addition of the end-blocking agent, it is heated to a high temperature of 250 to 360 ° C. Therefore, the obtained polymer has been inevitably colored, which is fatal for optical applications.
  • a method using an antioxidant is also known.
  • an antioxidant is added in the step of producing a predetermined polyarylate by interfacial polycondensation reaction between a divalent aromatic carboxylic acid halide and a divalent phenol comprising a biphenyl structure and a bisphenol structure.
  • a method for producing polyarylate, characterized by being added quantitatively, is disclosed (Patent Document 2). This method is relatively widely practiced as a secondary method for preventing color deterioration of industrial materials used for electronic materials and the like.
  • X is chlorine, bromine or iodine
  • R is a linear or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the alkyl group and the aryl Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group , An acyl group, an alkoxysulfinyl group, an alkylthiocarbonyl group, a thiosulfo group, a cyano group, a thiocyano group, an isocyano group, an isocyanato group, an isothiocyanato group, or a nitro group.
  • a phenyl group in which at least one hydrogen is substituted with fluorine an alkyl group in which at least one hydrogen is substituted with fluorine, and a phenyl in which at least one hydrogen is substituted with a chlorine or alkoxyl group Groups are mentioned.
  • fluorobenzoyl chloride, dodecanoyl chloride, chlorobenzoyl chloride and methoxybenzoyl chloride are used as compounds represented by X—C (O) —R.
  • a predetermined quaternary ammonium salt is used as a catalyst in an amount of 5 to 20 mol% based on the divalent phenol.
  • a method for producing polyarylate is disclosed in which monovalent carboxylic acid halide is added in an amount of 3 to 10 mol% based on dihydric phenol before the termination of interfacial polymerization (Patent Document 4).
  • the catalyst is not a catalyst having three or more butyl groups such as tributylbenzylammonium chloride and tetra-n-butylammonium bromide, which are conventionally used, but a quaternary compound having three or four ethyl groups.
  • Ammonium salt for example, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium hydroxide, triethylbenzylammonium hydrogensulfate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium hydrogensulfate It has been. In addition, the amount used is significantly larger than the conventional amount.
  • the present invention uses a large amount of such a special catalyst and adds a monovalent carboxylic acid halide just before the termination of the one-step reaction, and the residual monomer and its oxidant in the resulting polyarylate are obtained. It tries to reduce as much as possible.
  • the present invention provides an aromatic polyester that is hardly colored even after heat molding at a high temperature, retains remarkably high transparency, exhibits little birefringence, and also has high fluidity. To do.
  • the aromatic polyester obtained by the method described in Patent Document 3 has high heat resistance and transparency, and the aromatic polyester was hardly colored even by treatment at a high temperature. However, even though there was almost no coloration, it was not sufficient for use in optical applications. Accordingly, the present inventors have made various studies in order to obtain an aromatic polyester having higher transparency after the heat treatment. As a result, it has been found that it is necessary to increase the end-capping rate of the aromatic polyester with a substance listed as formula (II) in Patent Document 3, preferably benzoyl chloride.
  • the present inventors have further studied to obtain the aromatic polyester.
  • an aromatic polyester having a relatively large molecular weight was produced in the first stage, and in the subsequent stage, the terminal hydroxyl group present in the obtained aromatic polyester was further listed as the formula (II) in Patent Document 3.
  • the inventors have found that the above-mentioned predetermined aromatic polyesters can be produced by using a multi-stage method of imparting a known substance, preferably benzoyl chloride, and have completed the present invention.
  • it is preferable to purify the aromatic polyester obtained in the first stage by providing a purification step between the first stage and the second stage. Thereby, the relatively low molecular weight aromatic polyester contained in the aromatic polyester obtained in the first stage can be removed, thereby further increasing the terminal blocking rate of the obtained aromatic polyester. It can be done.
  • the present invention (1) In an aromatic polyester containing a polyhydric phenol residue and an aromatic polyvalent carboxylic acid, acid halide or acid anhydride residue thereof, the end of the aromatic polyester is represented by the following formula (I): -C (O) -R (I) (In the formula (I), R is an aliphatic group, an alicyclic group, a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group, a heterocyclic group, or a group consisting of a combination thereof.
  • At least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group.
  • R in the above formula (I) is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine, chlorine
  • R in the above formula (I) is a phenyl group, naphthyl group, anthranyl group, phenanthryl group or a group in which one hydrogen of these groups is substituted with fluorine, chlorine or methoxyl group, (1) to the aromatic polyester according to any one of (4), (7) R in the above formula (I)
  • Mw weight average molecular weight
  • the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 320 ° C., 10.0 kg load) is any one of the above (1) to (16), which is 15.0 or more.
  • Aromatic polyester (18) The melt flow rate (MFR, unit: g / 10 min, measurement condition: 320 ° C., 10.0 kg load) is 30.0 or more, and is described in any one of (1) to (16) above Of aromatic polyester, (19) The melt flow rate (MFR, unit: g / 10 min, measurement condition: 320 ° C., 10.0 kg load) is 50.0 or more, and is described in any one of (1) to (16) above Of aromatic polyester, (20) The melt flow rate (MFR, unit: g / 10 min, measurement conditions: 320 ° C., 10.0 kg load) is 60.0 or more, and is described in any one of (1) to (16) above Of aromatic polyester, (21) The above (1) to (20), wherein the polyphenol is bisphenol A, and the aromatic polycarboxylic acid, its acid halide or acid anhydride is terephthaloyl dichloride and / or isophthaloyl dichloride. An aromatic polyester according to any one of the following: (22) The aromatic polyester according to any one
  • the present invention also provides (24) (i) In a method for producing an aromatic polyester by reacting a polyhydric phenol with an aromatic polycarboxylic acid, its acid halide or acid anhydride, the aromatic polycarboxylic acid, its acid halogen 0 to 40 mol% of the following formula (II) with respect to the total charge of the compound or acid anhydride: XC (O) -R (II) (In the formula (II), X is chlorine, bromine or iodine, and R is an aliphatic group, alicyclic group, monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group, heterocyclic group.
  • At least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl A group that is substituted by a group, an alkoxysulfinyl group, an alkylthiocarbonyl group, a thiosulfo group, a cyano group, a thiocyano group, an isocyano group, an isocyanato group, an isothiocyanato group, or a nitro group)
  • the obtained aromatic polyester is reacted with the aromatic polyvalent carboxylic acid, its acid halide or acid anhydride in (i) with respect to the total charge of 3
  • a method for producing an aromatic polyester comprising a step of further reacting with ⁇ 80 mol% of a compound represented by the above formula (II).
  • Step (iii) is a purification of the aromatic polyester according to the above (40), wherein the solution containing the aromatic polyester is separated from the product solution after the reaction, and is subjected to the reaction of the step (ii).
  • step (iii) is purification by washing the product solution after the reaction to obtain a solution containing the aromatic polyester, and subjecting it to the reaction of the step (ii) Manufacturing method, (43) The method for producing an aromatic polyester according to (42), wherein the washing of the product liquid is performed with water, (44) The method for producing an aromatic polyester according to the above (40), wherein the step (iii) is purification by separating the aromatic polyester from the product solution after the reaction and subjecting it to the reaction of the step (ii), (45) In step (iii), a solution containing an aromatic polyester is obtained from the product solution after the reaction, and then the aromatic polyester is separated from the solution and subjected to the reaction of step (ii).
  • step (iii) the product solution after the reaction is washed to obtain a solution containing the aromatic polyester, and then the aromatic polyester is separated from the solution and used in the reaction of step (ii).
  • the method for producing an aromatic polyester according to (40), which is a purification to be provided (47) The method for producing an aromatic polyester according to the above (46), wherein the washing of the product liquid is carried out with water, (48)
  • the above (24) to (47) wherein the polyhydric phenol is bisphenol A, and the aromatic polycarboxylic acid, its acid halide or acid anhydride is terephthaloyl dichloride and / or isophthaloyl dichloride.
  • the method as described in any one can be mentioned.
  • the aromatic polyester of the present invention is remarkably high in transparency and hardly colored even after being processed at a high temperature, not only maintaining remarkably high transparency, but also having high fluidity. Yes. Therefore, the aromatic polyester of the present invention is extremely useful for optical applications such as optical fibers.
  • FIG. 1 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride.
  • Example 1 FIG. 2 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride.
  • FIG. 3 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride.
  • FIG. 4 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride.
  • Example 1 FIG. 5 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. (Example 5)
  • FIG. 6 is an NMR chart of an aromatic polyester end-capped with 1-naphthoyl chloride.
  • FIG. 7 is an NMR chart of a compound in which two hydroxyl groups present at both ends of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] are sealed with 1-naphthoyl chloride, respectively.
  • the aromatic polyester of the present invention has the following formula (I): -C (O) -R (I) (In the formula (I), R is an aliphatic group, an alicyclic group, a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group, a heterocyclic group, or a group consisting of a combination thereof.
  • At least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group.
  • R is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine
  • Preferred is a structure that is a group that is substituted by a chlorine, bromine, iodine, or alkoxyl group, where R is a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, or one hydrogen of these groups is fluorine, chlorine, or
  • a structure that is a group substituted with a methoxyl group is more preferable, and a structure that is a phenyl group, a naphthyl group, or a group in which one hydrogen of these groups is substituted with fluorine, chlorine, or a methoxyl group is still more preferable.
  • the higher the polyester end-capping rate the better.
  • the polyester end-capping rate is the structure represented by the formula (I) with respect to the sum of the number of polyhydric phenol residues present at the end of the aromatic polyester and the number of structures represented by the formula (I). Indicates the percentage of the number. Details of the measurement and calculation methods are given in the examples below.
  • the lower limit of the weight average molecular weight (Mw) of the aromatic polyester of the present invention is 3,000, preferably 5,000, more preferably 10,000, still more preferably 20,000, and even more preferably 25,000.
  • the upper limit is 1,000,000, preferably 500,000, more preferably 250,000, still more preferably 100,000, still more preferably 80,000, and particularly preferably 60,000. If it is less than the said minimum, it is not suitable for the use as an optical material.
  • the lower limit of the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 320 ° C., 10.0 kg load) of the aromatic polyester of the present invention is preferably 15.0, more preferably 30.0, still more preferably. 50.0, more preferably 60.0.
  • a higher melt flow rate value is preferable because molding becomes easier. Therefore, there is no particular limitation on the upper limit. If it is less than the said minimum, since shaping
  • the polyhydric phenol residue, aromatic polycarboxylic acid, acid halide or anhydride residue thereof contained in the aromatic polyester of the present invention, and the structure represented by the formula (I) produce an aromatic polyester.
  • it can be obtained by reacting a polyhydric phenol, an aromatic polyvalent carboxylic acid, an acid halide or acid anhydride thereof, and a compound represented by the following formula (II).
  • Polyhydric phenols and aromatic polycarboxylic acids, acid halides or acid anhydrides thereof are all known.
  • the aromatic polyester of the present invention is prepared by firstly (i) a method in which an aromatic polyester is produced by reacting a polyhydric phenol with an aromatic polyvalent carboxylic acid, an acid halide or an acid anhydride thereof. 0 to 40 mol% of the following formula (II) with respect to the total charged amount of the monovalent carboxylic acid, its acid halide or acid anhydride: XC (O) -R (II) (In the formula (II), X is chlorine, bromine or iodine, and R is an aliphatic group, alicyclic group, monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group, heterocyclic group.
  • At least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl A group that is substituted by a group, an alkoxysulfinyl group, an alkylthiocarbonyl group, a thiosulfo group, a cyano group, a thiocyano group, an isocyano group, an isocyanato group, an isothiocyanato group, or a nitro group) (Ii) the obtained aromatic polyester is reacted with the total amount of the aromatic polyvalent carboxylic acid, its acid halide or acid anhydride in (i).
  • R is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine.
  • a compound which is a group substituted by a chlorine, bromine, iodine or alkoxyl group, wherein R is a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group or one hydrogen of these groups is fluorine, chlorine, Or a compound that is a group substituted with a methoxyl group, and R is a phenyl group, a naphthyl group, or a compound in which one hydrogen of these groups is substituted with a fluorine, chlorine, or methoxyl group Are more preferable, and compounds in which R is a phenyl group or a naphthyl group are further preferable, and in particular, compounds in which R is a phenyl group are preferable.
  • X is preferably chlorine.
  • benzoyl chloride and naphthoyl chloride are preferable, and benzoyl chloride is particularly preferable.
  • the upper limit of the amount of the compound represented by the formula (II) used in the step (i) is 40 mol% with respect to the total charged amount of the aromatic polyvalent carboxylic acid, its acid halide or acid anhydride. , Preferably 30 mol%, more preferably 20 mol%, still more preferably 15 mol%, and the lower limit is 0 mol%, preferably more than 0 mol%, more preferably 4 mol%. If the above upper limit is exceeded, the weight average molecular weight of the resulting aromatic polyester will be low, and the aromatic polyester as the final product will not be suitable for optical applications.
  • the upper limit of the amount of the compound represented by formula (II) used in step (ii) is relative to the total charged amount of the aromatic polyvalent carboxylic acid, its acid halide or acid anhydride in step (i). 80 mol%, preferably 50 mol%, more preferably 35 mol%, still more preferably 20 mol%, and the lower limit is 3 mol%, preferably 5 mol%, more preferably 7 mol%, still more preferably 10 mol%. If it is less than the said minimum, a hydroxyl group may remain in the terminal of the aromatic polyester obtained, and coloring may be produced when it processes at high temperature. On the other hand, even if the above upper limit is exceeded, the amount of the compound represented by the formula (II) that can be incorporated into the end of the aromatic polyester becomes almost constant, and a significant improvement in coloring prevention after processing at high temperature cannot be expected.
  • reaction temperature is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., still more preferably 20 to 30 ° C.
  • reaction time is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, still more preferably. Is 30 to 90 minutes.
  • the reaction pressure is preferably 0.01 to 2 MPa, more preferably 0.08 to 0.12 MPa.
  • Manufacture can be either batch or continuous.
  • the conditions in step (ii) are the same as those in step (i) above.
  • step (ii) a predetermined amount of the compound represented by the formula (II) can be reacted at once, but the predetermined amount of the compound represented by the formula (II) is divided and used. And it can also be made to react in steps.
  • the charged amount of polyhydric phenol and aromatic polycarboxylic acid, acid halide or acid anhydride thereof is aromatic polycarboxylic acid, acid
  • the polyhydric phenol is preferably 1.0 mol or more, more preferably 1.0 to 5.0 mol, and more preferably 1.1 to 3. mol based on 1.0 mol of the halide or acid anhydride. More preferably, it is 0 mol.
  • steps (i) and (ii) conventionally known catalysts can be included in known amounts.
  • a quaternary ammonium salt represented by the following formula can be used as the catalyst.
  • the amount of the catalyst added is preferably 0 to 10 mol%, more preferably 0.001 to 5 mol%, based on the amount of charged polyphenol in step (i) in both steps (i) and (ii), More preferably, it is 0.005 to 1 mol%.
  • Y represents H, an ethyl group, a butyl group or a benzyl group
  • X represents Cl, Br, I, OH or HSO 4
  • n is an integer of 1 to 8, preferably 3 to An integer of 8 is shown.
  • Examples of the quaternary ammonium salt include tetrabutylammonium fluoride, tetrabutylammonium fluoride hydrate, tetraethylammonium fluoride hydrate, tetraethylammonium fluoride tetrahydrofluoride, tetraethylammonium fluoride trihydrofluoride, Tetrabutylammonium chloride, tetrapropylammonium chloride, tetrapentylammonium chloride, acetylchlorin chloride, (3-acrylamidopropyl) trimethylammonium chloride, benzalkonium chloride, benzoylchlorin chloride, benzylcetyldimethylammonium chloride hydrate, N-benzylcinchone Nidium chloride, benzyldimethylphenyl ammonium Chloride, benzyldimethylstearylammonium chloride, benz
  • tetra-n-butylammonium bromide tetrabutylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrapentylammonium bromide, tetrapentylammonium chloride and the like are preferably used.
  • the method for producing an aromatic polyester of the present invention further includes a step (iii) of purifying the product solution obtained after the reaction obtained in the step (i) between the steps (i) and (ii). Can do.
  • the purification in step (iii) includes purification for separating the solution containing the aromatic polyester from the reaction product produced in step (i), and from the reaction product produced in step (i).
  • separates aromatic polyester itself is mentioned. In the former purification, the solution containing the obtained aromatic polyester is fed to the reaction of step (ii), while in the latter purification, the obtained aromatic polyester itself is fed to the reaction of step (ii). Is done.
  • the method for carrying out these purifications is not particularly limited, and conventionally known methods can be used.
  • the product solution after the reaction produced in the step (i) is preferably water, for example, A method is used in which a solution containing an aromatic polyester, preferably an organic phase containing an aromatic polyester, is obtained by washing with ion exchange water.
  • the reaction product produced in step (i) is preferably water, for example, A method of washing with ion exchange water to obtain a solution containing an aromatic polyester, preferably an organic phase containing an aromatic polyester, and then separating the aromatic polyester from the solution is used.
  • a method for separating the aromatic polyester from the solution for example, a method is used in which the solution is mixed with a solvent containing alcohol such as methanol to precipitate the aromatic polyester, which is filtered and separated. be able to.
  • polyhydric phenol various known polyhydric phenols such as divalent, trivalent and tetravalent can be used.
  • 2,2′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A], 2,4′-dihydroxydiphenylmethane, bis- (4-hydroxyphenyl) methane, bis- (2-hydroxyphenyl) methane, bis- (4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,2-bis- (4-hydroxyphenyl) ethane, 1,1-bis- ( 4-hydroxy-2-chlorophenyl) ethane, 1,1′-binaphthal
  • 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable, and other compounds containing a wholly aromatic hydroxyl group having a rigid molecular structure containing no alkylene chain in the main chain,
  • bisphenol A 2,2′-bis- (4-hydroxyphenyl) propane
  • other compounds containing a wholly aromatic hydroxyl group having a rigid molecular structure containing no alkylene chain in the main chain For example, biphenols, binaphthalenediols, dihydroxynaphthalenes, dihydroxyfluorenes, dihydroxyoxofluorenes, catechols, resorcinols, hydroquinones and the like are preferably used.
  • aromatic polyvalent carboxylic acid various known aromatic polyvalent carboxylic acids such as divalent, trivalent and tetravalent can be used.
  • phthalic acid dimethyl phthalate, diphenyl phthalate, isophthalic acid, dimethyl isophthalate, di (cyanomethyl) isophthalate, diphenyl isophthalate, di (2,4-dinitrophenyl) isophthalate, isophthalic acid (1,1- Dioxobenzothiophen-3-yl), di (3-benzoisoxazolyl) isophthalate, di (2-benzothiazolyl) isophthalate, isophthalic acid (1-benzotriazolyl), dithioisophthalic acid S, S ′ -Dipropyl, dithioisophthalic acid S, S'-di (p-nitrophenyl), dithioisophthalic acid S, S'-di (2-benzoxazolyl), dithioisophthalic acid S,
  • wholly aromatic polycarboxylic acids having a rigid molecular structure not containing an alkylene chain in the main chain such as phthalic acids, terephthalic acids, isophthalic acids, biphenyldicarboxylic acids, naphthalenedicarboxylic acids, oxofluorenedicarboxylic acids, Anthracene dicarboxylic acids, anthraquinone dicarboxylic acids, biphenylene dicarboxylic acids, terphenyl dicarboxylic acids, quaterphenyl dicarboxylic acids, azobenzene dicarboxylic acids, furandicarboxylic acids, thiophenedicarboxylic acids, pyrandicarboxylic acids, dibenzofurandicarboxylic acids, dibenzothiophenedicarboxylic acids, xanthenedicarboxylic acids Acids, dibenzo [1,4] dioxin dicarboxylic acids, phenyldicarboxy
  • the acid halide or acid anhydride of said aromatic dicarboxylic acid can also be used.
  • the acid halide of aromatic dicarboxylic acid include phthaloyl dichloride and naphthoyl dichloride. Of these, preferably phthaloyl dichloride, such as isophthaloyl dichloride or terephthaloyl dichloride, is used.
  • melt indexer F-W01 (trademark) manufactured by Toyo Seiki Seisakusho was used.
  • a temperature of 320 ° C. and 10.0 kg load was measured as a standard
  • the temperature was 260 ° C. and 10.0 kg.
  • the load was measured as a standard.
  • polyester end sealing rate When measuring the polyester end-capping rate, an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. was used. In the NMR analysis, the polyester end-capping rate has the methyl proton peak (2) (around 1.75 ppm) of the bisphenol A residue contained in the aromatic polyester, and the bisphenol A residue present at the end of the aromatic polyester.
  • the peak (3) and the peak (4) were used as indicators of a bisphenol A residue having a benzoyl group end contained in an aromatic polyester.
  • the polyester end-capping rate is the sum of the area ratios of the above peak (3) and peak (4), and the area ratio of the above peak (3) and peak (4) and the area ratio of peak (1). The value divided by the total is shown as a percentage.
  • Example 1 the area ratio of the peak (2) observed near 1.75 ppm is 6.0 (not shown), and the area ratio of the peak (1) recognized near 6.73 ppm is The area ratio of peak (3) observed at 7.415 to 7.53 ppm and peak (4) observed from 8.16 to 8.18 ppm is 0.10648 and 0.13454, respectively. . Assuming that all bisphenol A residues are 1, the number of bisphenol A residues having a hydroxyl terminal is 0.002075 (0.00415 / 2) from the area ratio of peak (1).
  • Example 1 In a 500 milliliter eggplant-shaped flask equipped with a stirrer, 200 milliliters of water was added, and 0.78 grams (19.5 mmol) of sodium hydroxide and 0.049 grams (0.15) of tetra-n-butylammonium bromide were added. Mmol) and dissolved with sufficient stirring.
  • Example 2 0.639 g of benzoyl chloride (4.5 mmol, 7.5 mol with respect to the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I)
  • the aromatic polyester was obtained in the same manner as in Example 1 except that the aromatic polyester was changed.
  • Example 3 0.852 grams of benzoyl chloride (6.0 mmol, 10.0 mol for the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I)
  • the aromatic polyester was obtained in the same manner as in Example 1 except that the aromatic polyester was changed.
  • Example 4 1.064 grams of benzoyl chloride (7.5 mmol, 12.5 moles relative to 0.0606 moles of the total required amount of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I)
  • the aromatic polyester was obtained in the same manner as in Example 1 except that the aromatic polyester was changed.
  • Example 5 In a 500 milliliter eggplant-shaped flask equipped with a stirrer, 200 milliliters of water was added, and 0.78 grams (19.5 mmol) of sodium hydroxide and 0.049 grams (0.15) of tetra-n-butylammonium bromide were added. Mmol) and dissolved with sufficient stirring.
  • FIG. 1 H-NMR measurement of the aromatic polyester is shown in FIG.
  • an FT-NMR apparatus JNM-EX270 (trademark) manufactured by JEOL Ltd. was used as the NMR apparatus. From the 1 H-NMR chart of FIG. 5, absorption peaks (7) and (8) derived from hydrogen of the incorporated benzoyl group [4-H near 7 ppm (p-position with respect to ester group (4-position)) (Protons present in FIG.
  • Example 6 0.426 grams of benzoyl chloride (3 mmol, 6.6 mol% with respect to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) Aromatic polyester was obtained in the same manner as in Example 5 except that it was changed to (1).
  • Example 7 0.639 grams of benzoyl chloride (4.5 mmol, 9.9 mol with respect to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II)
  • the aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.
  • Example 8 0.852 grams of benzoyl chloride (6.0 mmol, 13.2 mol relative to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II)
  • the aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.
  • Example 9 1.064 grams of benzoyl chloride (7.5 mmol, 16.5 moles relative to the total charge of 0.04546 moles of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II)
  • the aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.
  • Example 1 represents bisphenol A
  • FC represents both terephthaloyl dichloride and isophthaloyl dichloride (1: 1 mixture)
  • BC represents benzoyl chloride.
  • Each mol% is calculated as a ratio to FC 100 mol%.
  • the MFR value is a value measured at a temperature of 320 ° C. and a 10.0 kg load in Examples 1 to 4 and Comparative Examples 1 and 2, and in Examples 5 to 9 and Comparative Examples 3 to 4, the temperature is 320 ° C. It was a value measured at a temperature of 260 ° C. and a 10.0 kg load because it was extremely large and could not be measured when measured at a load of 0.0 kg.
  • Comparative Example 5 is a one-step reaction. In Comparative Example 5, the MFR value was remarkably high because the weight average molecular weight was low, and measurement was impossible even at a temperature of 260 ° C. and a 10.0 kg load.
  • Comparative Example 1 was one in which benzoyl chloride was not added in any of steps (i) and (ii), and Comparative Example 2 was not added benzoyl chloride in step (i).
  • ii benzoyl chloride is added within the range of the present invention. In any case, the absorbance was remarkably bad, it was found that the heat deterioration was poor, and the coloring after the heat treatment was remarkable.
  • Comparative Example 3 was obtained by adding no benzoyl chloride in the stage (ii), and Comparative Example 4 was obtained by adding benzoyl chloride in the stage (ii) within the range of the present invention.
  • the absorbance was remarkably bad, it was found that the heat deterioration was poor, and the coloring after the heat treatment was remarkable.
  • the aromatic polyester of the present invention cannot be obtained even if the two-step reaction is employed unless the reaction is carried out using a predetermined amount or more of benzoyl chloride in the step (ii).
  • Comparative Example 5 an aromatic polyester was produced using a one-step reaction.
  • the aromatic polyester described in Patent Document 3 is not an aromatic polyester having a high molecular weight, a high end-capping rate, and a very low coloration after heating, like the aromatic polyester of the present invention. That means.
  • Example 10 A reaction vessel equipped with a stirrer was prepared, and the inside of the reaction vessel was replaced with nitrogen gas. Subsequently, 1.1 liters of water was placed in the reaction vessel, and further, 37.67 grams (0.165 mole) of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], sodium hydroxide 14.0 Gram (0.35 mol) and 24.18 milligrams (0.075 mmol) of tetra-n-butylammonium bromide as a catalyst were added and dissolved with sufficient stirring.
  • tetra-n-butylammonium bromide used as a catalyst was 0.05 mol% based on the total amount of bisphenol A.
  • the entire amount of the substance in the latter container was added dropwise to the former reaction container over 5 minutes, and the mixture was stirred and mixed at 25 ° C. for 30 minutes to react.
  • the organic layer was extracted from the total amount of the substance in the reaction vessel and separated. The separated organic layer was washed 3 times with 300 ml of water.
  • the organic layer was dropped into a mixed solvent of 4 liters of methanol and 250 ml of water under stirring to precipitate a polymer. The precipitated polymer was recovered by filtration, and then dried at 120 ° C. under reduced pressure for 12 hours in a vacuum dryer to obtain 57.7 g of aromatic polyester (yield 97%).
  • step (ii) A solution dissolved in 20 ml of methylene was added dropwise over 1 minute, and the reaction was continued by further stirring for 1 hour. After completion of the reaction (reaction in step (ii)), the organic layer was extracted from the total amount of substances in the reaction vessel and separated. The separated organic layer was washed 3 times with 50 ml of water. Next, the organic layer was dropped into a mixed solvent of 400 ml of methanol and 25 ml of water with stirring to precipitate a polymer. The precipitated polymer was collected by filtration, and then dried at 120 ° C. for 12 hours under reduced pressure in a vacuum dryer to obtain 5.69 grams of aromatic polyester.
  • the obtained aromatic polyester had a weight average molecular weight of 40,000 and a terminal blocking rate of 99.6%.
  • the MFR value was 1.26 g / 10 min as measured at a temperature of 260 ° C. and a 10.0 kg load, which was good. When measured at a temperature of 320 ° C. and a load of 10.0 kg, it was extremely high and could not be measured.
  • Example 11 Example 1 except that the amount of tetra-n-butylammonium bromide used in the reaction of step (i) was changed from 24.18 milligrams (0.075 millimoles) to 14.51 milligrams (0.045 millimoles). This was carried out in the same manner as in 10.
  • the weight average molecular weight of the obtained aromatic polyester was 24,000, and the end capping rate was 99.3%. Also, the MFR value was 22.4 g / 10 min as measured at a temperature of 260 ° C. and a 10.0 kg load, which was good. When measured at a temperature of 320 ° C. and a load of 10.0 kg, it was extremely high and could not be measured.
  • the end capping rate of the aromatic polyester is measured as follows.
  • an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. was used. Peak of two protons present in the 1-naphthoyl chloride residue of the bisphenol A residue present at the end of the aromatic polyester (11) (proton present in the 5-position with respect to the ester group, around 7.95 ppm) And peak (12) (proton present at 4-position with respect to ester group, around 8.13 ppm), and at ortho position relative to hydroxyl group of bisphenol A residue present at the end of aromatic polyester The calculation was based on the peak of two protons (13) (around 6.73 ppm).
  • the peak (13) is used as an index of all bisphenol A residues contained in the aromatic polyester, and the peak (11) and the peak (12) are 1-naphthoyl chloride contained in the aromatic polyester. It was used as an indicator of bisphenol A residues having a base end.
  • the polyester end-capping rate is the sum of the area ratios of the peak (11) and peak (12), and the area ratio of the peak (11) and peak (12) to the area ratio of the peak (13). The value divided by the total is shown as a percentage.
  • the NMR chart of the aromatic polyester obtained in Example 10 was shown.
  • the area ratio of the peak (11) observed near 7.95 ppm is 0.0609
  • the area ratio of the peak (12) recognized near 8.13 ppm is 0.0714
  • the area ratio of the peak (13) is 0.0005.
  • the number of bisphenol A residues having a hydroxyl terminal is 0.00025 (0.0005 / 2) from the area ratio of the peak (13).
  • the number of bisphenol A residues having 1-naphthoyl chloride terminal is 0.06615 [(0.0609 + 0.0714) / 2]. From these results, the end capping rate was calculated to be 99.6% [0.06615 ⁇ 100 / (0.06615 + 0.00025)].
  • each peak was assigned to two hydroxyl groups present at both ends of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A].
  • Each compound was sealed with 1-naphthoyl chloride and determined based on NMR measurements of the material.
  • the apparatus used was an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. as described above.
  • FIG. 7 shows the chart and each attribution.
  • the aromatic polyester of the present invention not only has heat resistance, but is difficult to be colored at the time of molding, not only has excellent optical properties, but also has high fluidity. Therefore, it is extremely useful not only for optical fibers but also for optical applications such as lenses, optical elements, and display substrates. In addition, it can also be used for materials that particularly require heat resistance, such as automobile parts and electronic precision parts.
  • Peak of two protons present in the ortho position relative to the hydroxyl group of bisphenol A residue 2 Peak of methyl proton of bisphenol A residue 3 Two protons present in benzoyl chloride residue of bisphenol A residue Peak 4 (proton present in m-position (3,5-position) with respect to ester group) Two protons present in benzoyl chloride residue possessed by bisphenol A residue (o-position relative to ester group) (Proton present at (2,6-position)) Peak 5 of isophthaloyl dichloride 6 Peak of terephthaloyl dichloride 7 Peak of benzoyl chloride 8 Peak of benzoyl chloride 11 The bisphenol A residue present at the end of the aromatic polyester has Protons present in the 1-naphthoyl chloride residue Peak 12 of proton (existing in 4-position with respect to the ester group) present in the 1-naphthoyl chloride residue possessed by the bisphenol A residue present at the end of the aromatic polyester. Peaks of two protons that are ortho

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WO2014160333A1 (en) * 2013-03-13 2014-10-02 Liquid Thermo Plastics, Inc. Methods for preparation of polyester via base catalysis
WO2016052748A1 (ja) * 2014-10-03 2016-04-07 株式会社カネカ ポリカーボネート用およびポリアリレート用流動性向上剤、ポリカーボネート樹脂組成物、ポリアリレート樹脂組成物、並びにその成形品
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US20200040180A1 (en) * 2016-04-06 2020-02-06 Kaneka Corporation Polycarbonate resin composition and molded article thereof
EP3848415A4 (en) * 2019-07-26 2021-10-06 Kinte Materials Science and Technology Co., Ltd. POLYESTER RESIN AND PROCESS FOR ITS MANUFACTURING, COATING AND WORKPIECE
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